Clear and pigmented oil-in-water resin emulsions



, done with dyestuffs, which Patented June 15, 1954 OFFICE CLEAR AND PIGMENTED -OIL-IN- WATER RESIN EMULSIONS Laszlo Auer, South Orange, N. J.

No Drawing. Application November 20, 1950,

Serial No. 196,724

20 Claims.

1 GENERAL OUTLINE OF INVENTION Textile printing and dyeing is conventionally are water soluble or are developed on the fibers from water soluble intermediates. The application of dyestuffs is a multistep process and frequently the ultimate color is not visible at the stage when the fabrics leave the printing or dyeing machinery. This causes difiiculties in control and to avoid seconds needs great skill and lots of luck too. Dyestuffs, in general, have more or less limited light fastness, particularly in light or pastel shades. Fade-o-meter is an accepted apparatus to measure light fastness in an accelerated manner. Whereas automobile lacquers or resin finishes are required to be fast to Fade-o-meter exposure for 1000 hours, dyed fabrics or fabrics printed with dyes, fade in less than 48 hours, in most cases, and to hours exposure fastness has to be accepted with many shades. Pigments, in general are more light fast than dyes, and therefore pigment printing and pigment dyeing was the aim of the art since quite some time. As pigments are dry powders and insoluble in water or organic solvents, they have to be adhered to the fabric by a resinous binder. A particularly successful binder for pigments was found in the combination of oil modified alkyd resins and organic solvent soluble amino-aldehyde resins, such as butyl modified urea formaldehyde resins or butyl modified melamine formaldehyde resins. For printing, water-in-oil emulsion colors are used, whereas for solid color dyeing, it is customary to use oil-in-water emulsions. The oil phase sists of the binder resin, usually comprising an alkyd resin component and an amino-aldehyde resin component, in the presence or absence of organic solvents. The pigments may be incorporated either in the oil phase or the water phase.

The general drawback of pigment colors is their crocking. Crocking is marking oh: by abrasion to an unprinted and not dyed portion of the fabric, or to fabric in general. The crocking of pigment colors is their main drawback, which prevents increase in their use for coloring textiles. Also, the washability and dry cleaning resistance of pigment colored fabrics requires improvement, particularly if high temperatures of curing is to be avoided. Textile plants have low pressure steam available and for curing or thermosetting the amino-aldehyde resins temperatures of 275 to 300 F. are needed.

of such emulsions con- In present day textile printing with pigments water-in-oil emulsions are used in the trade, in spite of the fact, that solvent cleaning of equipment is troublesome in textile plants.

Oil-in-Water emulsions are easier to handle in textile plants than water-in-oil emulsions. They could be washed from the printing rollers, color boxes, doctor blades, brush rollers, etc. with water. They also could be washed from backgrays, rubber blankets with case. There are two'reasons why there was no oil-in-water type printing color on the market prior to the instant development: (1) emulsifying agents which are suitable to produce oil-in-water emulsions and the necessary protective colloids, which secure stability, both reduce the washability of pigment prints. Present day binders do not take such reduction successfully. (2) If the same quantity of pigment color is dispersed in an oil-inwater emulsion color concentrate and in a waterin-oil color concentrate, and both are reduced in varying proportions with clear cut-back emulsions, the water-in-oil emulsion printing colors take more reduction to yield a certain shade, than oil-in-water emulsions. The reason is probably explained by the fact that most pigments are hydrophobic and organophilic, flush into the oil phase, and if the color bearing oil phase is the continuous phase of the emulsion, better mileage is obtained, pound for pound of color. As the pigment colors are the most expensive ingredient of printing emulsion colors, economic factors excluded up to now the use of oil-in-water emulsions for printing, whereas they are used regularly for pigment padding, to obtain solid shades.

In accordance with this invention, improve ment is achieved in making oil-in-water emulsion pigment colors by using fatty acid ester resin binders which are emulsion polymerized or emulsion aggregated. The instant invention is a continuation-in-part of copending applications Serial Nos. 739,945, filed April 7, 1947, now Patent 2,530,370; 91,009, filed May 2, 1949: 169,791, filed June 22, 1950; and 180500, filed August 21, 1950. By the use of such resin binders advantages result in faster solidifying binders, increased toughness and better aging qualities of the prints obtained.

As binder resins the following may be mentioned as suitable: alkyd resins, condensation products of bis-phenol and epichlorhydrin esterified with fatty acid esters, styrenated alkyds, styrenated oils, pentaerythritol esters of fatty acids, which may be advantageously premon- 3 densed with maleic anhydride, amongst others. Organic solvent soluble urea and melamine formaldehyde resins may be present in the emulsions to further toughen the binder resins.

The emulsion polymerized or emulsion aggregated oil-in-water emulsions of fatty acid esters are described in my copending application Serial No. 739,945, now Patent 2,530,370, above referred to. To prepare such emulsions, the fatty acid esters are bodied to and then emulsified. The dispersed phase of such emulsions is the fatty acid ester. The dispersed phase particles of such emulsions are then aggregated by employing hydrogen peroxide, or in other ways as described in said copending application;

The degree of aggregation of the dispersed partic es in situ is such as torender the emulsion highly sensitive to the action of air when spread in thin films and thereby provide for the formation of a coherent soiid film immediately upon demulsiflcation of the emulsion. Advantageously the pH value of the emulsion is retained within certain limits during the aggregation treatment. Improved results are obtained by the treated emulsions of this specification if the increase in oxygen content of the solidified fatty acid esters is kept low, when compared with the oxygen content or the same esters before emulsiiication and emulsion aggregation.

STARTING MATERIALS Whereas fatty oils which are drying or semidrying maybe used in this process, providin requirements on chemicalresistance of the binders is moderate, it is preferred to use esters of fatty acids which yield tougher films than drying oils. Typical of the oils, the fatty acids of which may form the esters used in this process are as follows:

Tung oil Oiticica oil Dehydrated castor oil Linseed oil Perilla oil Sunflower oil Poppyseed oil Soya bean oil Walnut oil Rapeseed. oil Pineseed oil Olive oil Corn oil Cottonseed oil Coconut oil Babassu oil Hydroxylated oils such as castor oil, etc. Fish oils (train oils) The following polyhydric alcohols are suitable for producing esters with the above fatty acids: Glycerin Pentaerythritol Mannitol Sorbitol Alcohols formed by the condensation of bisphenol and epichlorhydrin Certain polyglycols, amongst others.

To form fatty acid modified alkyd resins, the following polycarboxylic acids and their anhydrides may be used:

Phthalic acid, Maleic acid, Succinic acid, Malic acid.

a relatively heavy viscosity i Very excellent results can be obtained by styrenated alkyds which are copolymers of fatty acid.

modified alkyd resins and polystyrene. Styrenated fatty oils, such as styrenated linseed and soyabean oil, or styrenated dehydrated castor oil yield also interesting products.

Very satisfactory results have been obtained with pentaerythritol esters of fatty acids which may be advantageously precondensed with maleic anhydride. Particularly advantageous results were obtained with the condensation products of bis-phenol and epichlorhydrin, esterified with fatty acids, such as dehydrated castor oil fatty acids or mixtures of the fatty acids of soyabean oil and oiticica oil. Such esters may be further modified by styrenating them.

The above described fatty acid ester may be toughened by the addition of organic solvent soluble amine aldehyde resins with urea or melamine or alkylated or etherifled urea and melamine. l

A few examples are given of commercially manufactured resins useful in the instant process:

1) Epichlorhydrin and bis-phenol condensa tion product (alcohol): Epon 190 i. Dehydrated castor oil fatty acid ester of Epon 1004: Epitex 120.

(2) Styrenated alkyd: Styresol 4256.

(3) Phthalic anhydride-free styrenated alkyd: Soya fatty acid ester of Carbic Anhydride (Bicyclo 2-2-1 Cycloheptane delta 5 dicarbo-Xylic anhydride 2,3) and glycerine (co-ester of fatty acids and anhydride), styrenated, BJS 502, RJS 153 and RJS 155 resins. Polystyrene content 25 to 75 (s) Pentaery'thritol-glycerin mixed ester of maleic anhydride treated fatty acids: Esskol, linseed oil base.

(5) Styrenated soyabean oil: Keltrol 60.

Organic solvent soluble amine-aldehyde resins: Melmac 245-8, Melmac 248-8;

The polyhydric alcohols, forming the esters useful as starting materials in this process, should be preferably at least tri-hy-dric, such as glycerin.

I found that in my process best results are obtained with polyhydric alcohol esters of acids of fatty oils, which esters contain in their acid component at least 50% acids of fatty oils and which fatty oil acids comprise fatty acids having at least two double bonds. In this definition of fatty acid esters, there is included the group of drying and semi-drying fatty oils, further the group of synthetic oils and the group of alkyd resins, not containing more than 50% polybasic acids in their acid component.

Any appropriate mixtures or combinations of members of the above described classes may be treated, as desired.

The better drying a fatty oil is, the more suitable it is for my present process. I found that at least some of the fatty acids present in my esters should preferably contain more than one double bond in the molecule. This includes esters of the drying oil fatty acids and of the semi-drying oil fatty acids. I also found that esters of fatty acids having conjugated double bonds undergo easier my emulsion aggregation process, than fatty acids with isolated double bonds.

EMULSION AGGREGATION The fatty acid esters are bodied to a suitable viscosity before emulsification, and my copending application Serial No. 739,945, now Patent 2,530,- 370 describes the ammonia test which is very suitable to determine satisfactory viscosity. The sulfur test described in the same specification is another suitable method.

The emulsion polymerization or emulsion aggregation process and its reaction conditions is described in detail in copending application Serial No. 739,945, now Patent 2,530,370. The aggregating agent is oxygen. I believe that the active agent of my. process is an electrically charged oxygen particle. However, I have no definite proof of that supposition. As not any and all oxygen may act in my process as aggregating agent, I shall refer to the oxygen which is suitable in my process as active oxygen and I believe that the particles of most probably electrically charged.

I can obtain my active oxygen in various ways. (1) I may use a peroxide, such as a metal peroxide or hydrogen peroxide, or an organic peroxide to supply my active oxygen to my emulsions. I may blow oxygen or an oxygen containing gas, such as air, through my emulsions. use the oxygen which is present in the water phase of my emulsion as absorbed oxygen.

Application of heat accelerates the action of the oxygen. Usually temperatures between 50 C. and 80 C. are useful for such acceleration. Agitation of the emulsion also accelerates the process.

In case peroxides are used and oxygen is libtemperatures lower than room temperature.

The concentration of the emulsion influences the rate of reaction. The to non-volatile containing emulsions will produce solidified particles faster than a 70% solid content emulsion. Very satisfactory results can be obtained around non-volatile content.

ADVANTAGEOUS PH LIMITS One of the important criterions of my process is the pH of the emulsion. I found that it is important to have critical pH limits to carry out my process satisfactorily. I found that the reaction is extremely slow with a pH of 7 and there is a very slow range from about a pH of 5.7 to about 8.4. The range is very active below 5.7, such as for instance in the neighborhood of pH of 2.8 and also above 8.4, for instance in the region of pH of 10.5 and higher. In other words, the reaction is greatly accelerated by the pH values below 5.7 or above 8.4. However, for many purposes, if working on the alkaline side, I found it to be advantageou to have a pH of at least 10, and if working on the acid side, tohave a pH which does not exceed 4.

It has been found that metallic driers are accelerating the emulsion aggregation process particularly in such cases in which the aggregation is carried out in an alkaline medium. Therefore, if metallic driers are desired to be present in the fatty acid esters, it is of advantage to work on the alkaline side. However, if the absence of this active oxygen are metallic driers is desired, a conversion in an emulsion on the acid side is more desirable. Further, it may be mentioned that conversion on the acid side is advantageous if a constant pH is desired. In case of emulsion aggregation on the alkaline side, the pH generally changes insofar as it gradually becomes lower.

In the illustrative examples of this specification, the process will be demonstrated on emulsions which are on the alkaline side of the pH range. This is meant to illustrate the process only and not to limit same.

OXYGEN SUPPLYING AGENTS As mentioned further above, if other reaction conditions are proper, the oxygen content of the water, present in the emulsion, may be satisfactory.

Oxygen may be supplied to the emulsion in form of oxygen gas or oxygen containing gases, such as air, by bubbling through the emulsion such gases or by introducing them by known means. Ozone may also be used.

To produce oxygen in situ peroxides or other per-compounds may be used. In most of the examples hydrogen peroxide is used to illustrate the addition of per-compounds. However, other peroxides may also be used, such as sodium peroxide, barium peroxide, magnesium peroxide, zinc peroxide, other metal peroxides, or organic peroxides, such as benzoyl peroxide, urea peroxide, Examples of per-compounds are further perborates, percarbonates, persulfates, such as potassium, sodium and ammonium persulfates, perchlorates, pyrophosphate peroxides, ozonides, etc. The criterion of the usefulness of these agents is that they should supply oxygen in situ under the reaction conditions applied in my process and that the emulsion could be prepared in r f such a way that it should not break in their pres- OXYGEN CONTENT In my process the oxygen content of the emulsilied fatty acid esters increase very little, if any,

during the emulsion aggregation process. oxygen content increase is not more than. 2.8%

and advantageously not more than 1 In most cases the oxygen content increase is less than EMULSIFYIN G AGENTS Trade Name Manufacturers Description r M Duponol ME Fatty alcohol sulphate, sodium salt. Aerosol O'I Dloctiyl ester of sodium sulphosucciuic aci Emulphor AG.. Polyethyleneoxide condensation product. Beta Sol Quaternary ammonium salt.

Igepon. Sodium sulphonate of an oleic acid 'ester of an aliphatic compound, for instance, of

Triton 720 and 770..- Sodium salt of aryl alkyl poly ether sulphonatc.

Emulgor A A highly polymerized glycol ester.

m I found that from the various emulsifying agents such types are most suitablawhich are ac- PIGMENTS USED IN MAKING HATER DISPERSIONS The organic pigments used herein are usually prepared by precipitation methods. They are'all water insoluble. As starting material for this invention either a filter press cake or dry powder can be used. Carbon black, if used, is not made by precipitation method and is used as dry powder in the process.

The following groups of pigments are exempliiying, but not limiting the scope of the starting materials of this invention:

(1) PHTHALooYANINE PIGMENTS Phthalocyanine blue, which is a copper or tincopper phthalocyanine, is marketed under trade names of Monastral Fast Blue and as Heliogen Blue.

Phthalocyanine green, which is a chlorinated copper phthalocyanine color, i marketed under trade names oi": Monastral Fast Green, and as Heliogen Green.

(2) INSOLUBLE Azo PIGMENTS Benzidine yellows are couplings between dichlorobenzidine and acetoacetic arylides, such as the acetoacetic-anilide, -ortho toluidide, xylidide, -para chloro anilide and -ortho chloro anilide.

Benzidine orange is a coupling product of dichlorobenzidine with pyrazolone' substitution products, such as methyl phenyl pyrazolone.

l-lansa Yellows are acetoacetic arylide couplings with substituted anilines, like -ohloro 2-nitroaniline, or orthonitraniline, amongst others.

Insoluble Azo Beds are coupling products of the Naphthol- AS type compounds of beta-orthonaphthoic acid, such as Naphthol AS, Naphthol AS-OL, Naphthol ASeBS, Naphthol AS-D with fast color salts, such as.2,5 dichloroaniline, pnitro orthotoluidine, p nitro orthoanisidine, amongst others. One, example being the coupling product of Naphthol AS-ITR with HR Fast color salt. (Fast Red Color Salt ITR.)

Naphthol AS type couplings yield also yellows and oranges of the insoluble azo pigment group. Aniline Black pigment can be listed here too.

Toluidine maroon and Dianisidine Blue and a brown pigment obtained by forming the copper salt of paranitraniline red are other examples.

A newer color'is marketed as Monastral Fast Gold Green.

(3) VAT PIGMENTS Vat pigments are of the indigoid or anthraouinone type. The indigoid type includes thio- 81v ChemistryandPhysics ofOrganic Pigments, John Wiley & Sons, 1947.

Indanthrene Blue Color Index No. 1106, Schultz No. 837 is an example of the anthraquinone type vat pigments.

Structural formulas of some vat pigments are listed on pages 429 to 4:35 in volume V. of Mattiello': Protective and Decorative Coatings, John Wiley & Sons, Inc., New York, 1946. They include Indanthrene Rubine RD, Indanthrene Orange RRTA, Indanthrene Golden Orange GA, Indanthrene Brown RA, Hello Fast Yellow 60L, Indanthrone Brilliant Violet 33A, Fast Violet iRN, indigo Blue, Indanthrene Navy Blue RA.

The present dispersion method of this invention is applicable in vat pigment dispersions, which are not intended to be used as pigments, but applied for dyeing or printing in the textile industry also, which application includes forming a water soluble leuco compoundfrom the vat pigment and re-oxidizing same in a subsequent step. A better dispersion of the pigment in water willyield better results as far as color value is concerned, after reduction and re-oxidation. Conventional additives should be added, like now agents, hygroscopic agents, known in the art for this type of application.

(4) CARBON BLACKS Furnace Blacks, Channel Blacks, acetylene gas blacks and lamp blacks can also be dispersed byv the instant process.

PROTECTIVE COLLOIDS In the examples of this specification casein, methylcellulose and sodium carboxymethylcellulose are mentioned as suitable protective colloids. Dthers which may be used are: gum tragacanth, dextrin, starch solutions, sodium acrylate, sodium methacrylate, hydroxy ethylcellulose of the water soluble and alkali soluble types, locust bean gum, water soluble salts of the maleic adduct of styrene, etc. Alginates may be used also.

As far as protective colloids and emulsifying agents go, careshould be exercised, that anionic and non-ionic agents and systems may be mixed, and cationic agents and systems may be mixed with non-ionic agents and systems, but cationic andv anionic agents or systems normally cause flocculation of the emulsion or of the pigments. Ammonium caseinate, e. g. acts anionic, but it is possible to use casein in cationic systems, if it is dissolved-with the aid of cationic quaternary ammonium compounds.

C'ATIONIC EMULSIFYING AGENTS phase. Either the emulsion breaks or the pigment fiocculates, or both.

I have found very satisfactory results with lauryl ipyridinium chloride, ,cetyl-dimethyl-benzyl ammoniumchloride (Triton K-GO), methyl dodecyl benzyl trimethyl ammonium chloride (Hyamine 2389), amongst others. Theymay be used. as emulsifying agents to form oil-in-water resin emulsions and the first and last mentioned ones act as good pigment dispersing agents also.

EMULSIONS IN WOOD FINISHING In finishing wood filling properties of a coating are of great importance. Soft wood is more porous than hard wood and will absorb many coats of coating. Particular dimculty is observed with porous woods, like Douglas fir plywood, California redwood and the various pine woods.

I have found, that the emulsions of this invention, particularly the emulsion polymerized ones, will seal soft wood surfaces, will not raise grain. A clear coating of the emulsion will act as sealer under solvent type regular varnishes and pigmented emulsion undercoats will seal under solvent type or emulsion type top coats. They dry fast and recoating in 20 minutes to 2 hours is possible. They permit one day finishing systems with fast drying solvent type finishes as top coats. Some examples will be given further below, to show how such products act.

Proportions of ingredients-The proportions of the ingredients of the compositions of this inven tion, may tolerate certain limits. The examples here below illustrate the process and do not necessarily limit same.

Emulsifying agents.Normally 2 to 6% emulsifying agent is used, based on the dispersed As used herein, the expression the dispersed phase refers to the resin phase which may contain solvent, where the resin is in solvent solution. Occasionally larger proportions are of advantage and in some cases somewhat lower quantities may Work. As it will be seen in an example of the schematic type, 0.7% emulsifying agent is a typical example, based on the total resin emulsion.

Protective coZZoids.--Many protective colloids exert stabilizing properties in as low a proportion as of the water phase. The examples here below contain about 4 to 7% on the concentrated vention are stable to the degree, that they take repeated freezing and re-thawing cycles, without damage.

Resin content.The dispersed phase in many of the examples is close to 50%. If the dispersed phase consists of a resin in a 50% N. V. solution, the concentrated emulsion will contain about 25% resin. Depending on the fact, whether the resin is in solvent or solvent free, resin contents of 15% to 50% are possible in the binder emulsions of this invention.

5 Pigment conient.The pigment content in the color concentrates ranges from. 7 to 22%, but it may be higher if fillers or extender pigments are present. There is some limitation as far as the water content of presscakes is concerned, when presscakes form the starting material for the pigments. Most organic pigments are hydrophobic and presscakes come between 10% to 35% pigment content, depending on the nature of pigment and method of precipitation. However, if dry pigments, We can regulate the pigment slurries, properly disobtained as high as with '70 pigment content, the rest being water and dispersing agents. An example for this is a titanium dioxide dispersion in water.

Pigment to hinder ratio-4n the examples we have about 12 to 12 parts of resin solids and additional protective colloid solids per '7 to 22 parts of pigment. With pigments which crock persed, may be higher, larger binder proportions are required, whereas with pigments with low croclring properties, the binder quantity can be reduced.

In the case of wood finishing undercoats, the pigment content is much higher, as the nature of the product is different.

The color concentrate compositions of the present invention are viscous by nature and are dilutable with clear extender print paste emulsions to form the desired strength of shade when used for textile printing.

pH of emulsions-Great advantages can be obtained on acid side emulsion polymerization.

g. emulsions with metal free or drier-free formulation, can be successfully emulsion polymerized on the acid side, at pH ranges of 2.8 to 5. Such metal-free c ILLUSTRA'I'IVE EXAMPLES emulsifying agents work Also these require acid percentage of protective colloids will be considered variable, within the described scope of this specification.

E-PoLYnsTER BINDERS The E-polyester binders of this invention consist of an alcohol component and a fatty acid component.

Alcohol component of E-poZyesters.-The alcohol component of the E-polyesters of this invention are resinous condensation products of phenols, like p-HOCsH4)z-CMe2, Me being a methyl radical. The most common type of this group is represented by the condensation products of epichlorhydrin with bis-phenol. The following resinous alcohols can be prepared by such condensation:

Combining Melting Weight Point0.

These products are substantially free of halogens and should be considered as ethylene oxide derivatives of polynuclear phenols, showing hydroxy groups, which can enter into esterification reactions.

Fatty acid component of E-poZyesters.-The fatty acid components may be fatty acids of naturally occurring fats and fatty oils. Examples are: oleic acid, linoleic acid, linolenic acid, clupanodonic acid, dehydrated ricinoleic acid, eleostearic acid, natural mixtures of soyabean fatty acids, sunflower oil fatty acids, linseed oil fatty acids, dehydrated castor oil fatty acids, tung oil fatty acids, stearic acid, palmitic acid, lauric acid, tall oil acids, etc. Rosin may be used to replace part of the fatty acids. Normally these fatty acids have 12to 24 carbon atoms in the molecule. Unsaturated fatty acids obtained from drying and semi-drying fatty oils are preferred for this invention, as they reach the thermoset stage at room temperature or at low temperatures, not exceeding 220 at reasonable speed. Linseed. oil fatty acids and dehydrated castor oil fatty acids are examples of products with merit in this process. Rosin acids may be present to replace part of the fatty acids. E. g. linseed oil fatty acids and rosin may be combined simulta neously with the alcohol component.

RESINOUS E-POLYESTERS The following examples are given for the prep-- aration of the E-polyester binders, suitable in the instant process:

Example 1 iounds Alcohol component resin #2, with combining weight of 174 1102 Rosin, W. G. grade 243' Linseed oil fatty acids 1230 Petroleum aromatic solvent with boiling range from 318 to 100 F. and flash point of 100 F 680 Mineral spirits 681 Total 3936 Loss of water of esterification 205 Yield 3731 Heat to 4.80 acids and rosin,

Example 2 Pounds Alcohol component resin #2, with combining weight of 11a 25 i Dehydrated castor oil fatty'acids 1695 Xylol 3435 Total 7670 Loss of water of esterification 7 Yield 7270 Esterification reaction starts at 350 to 400 F.

l'taise temperature from 400 E. to 500 F. in 1% to 2 hours, pass inert gas through reaction mix ture, hold until acid number is 2. .Thin. Yield is 808 gallons, non-volatile 55%, 8.10 lbs/gal, acid number 0.5 to 2, viscosity'X to Z on Gardner scale. This resin is further reduced to 50% N. V.

' withxylol for use in the examples.

Example 3 42.15 parts of E-pclyester resin of Example 2, 0.31 part of mixed naphthenate driers, 12.22 parts of sodium lauryl sulfate solution in water, 20.65 parts of a casein solution in water,

container and add them slowly .to the resin solution containing mixture under agitation. Add the ammonium hydroxide solution and add finally the sodium carboxymethylcellulose solution. I-Iomogenize. This emulsion is a suitable binder for color concentrates.

Example 4 To a phthalocyanine green press cake, marketed under the trade name of Heliogen Green GV presscake, having 27.6% pigmentcontent Duponol ME dry powder was added to yield 18% Duponol on the pigment content, and Nekal A dry powder was added to yield 2% addition on the pigment content. The press cake wasmixed with a spatula by hand after 5 minutes it became completely liquid. It has .been found, that dry powder addition, which is attractive as it does not increase water content, yield very satisfactory results. However, the pre-mixing repre sents some problem and knife ,pronged agitators are needed, such as pony mixer the press cake to a slurry. Propeller types, or other turbine type agitators do not work well at this stage, as they could not manage tobreak up the lumps of the press cake. The pre-mix is then further dispersed by the aid of an Eppenbach Homomixer, which .is a high speed turbo mixer, having a narrow clearance between turbine and stator. It runs about 3,600 R. P. M. About 15 minutes .is satisfactory, but occasionally up to minutes maybe used. A 5 H. P. motored mixer satisfactorily disperses a 500 lb. press cake quantity in a to gal. size drum. head drum.) The active ingredient in Duponol ME- dry powder is the same as that of Duponol WA paste, 1. e. technical sodium lauryl sulfate.

The homomixed slurry is passed through a colloid mill, to complete dispersion and deflocculation. Pebble millingis also very satisfactory to complete pigment deflocculation and dispersion. 24 hours to 48 hours are satisfactory milling times.

Example 5 59 parts of the binder emulsion of Example '3, 26.25 parts of the phthalocyanine pigment dispersion in water of Example 4, 2.9 parts of a 60% polychloroprene latex, 3.9 parts of pine oil and 7.95 parts of water are mixed and homogen ized, to form a color concentrate. Other pigments may be used instead of the phthalocyanine blue, as described further above in Example 4.

Example 6 Example 3 is repeated, but using E-polyester resin solution of Example 1, after same has been reduced with mineral spirits to 50% non-volatile content. The resulting product is suitable as binder for color concentrates, like the one described in Example 5.

EMULSION PoLrMERIzED RESIN BINDERS If the resin binder is emulsion polymerized or emulsion aggregated, as described in my copending application Ser. No. 739,945, now Patent 2,530,370, to which this specification is'a conblades, to liquefy (Gpen gallon per pound, a flash Eaample 7 An emulsion-aggregated binder is prepared from the E-polyester solution of Example 2, according to Example 3, by the following changes: deducting 3.58 parts of the water added, and adding 3.58 parts of a 30 volume percent hydrogen peroxide solution to the emulsion at the stage after the ammonium hydroxide solution was added, but before the sodium carboxymethylcellulose solution is added. The hydrogen peroxide is added in increments, while the emulsion is slowly agitated. The addition of the hydrogen peroxide may be carried out during a 2 to 12 hours period. The sodium carboxymethylcellulose solution is added, after the emulsion aggregation process is completed.

Example 8 Example 7 is repeated with the change, that.

Example 9 A color concentrate is made of the product of Example 7, by first preparing a pigment grind from 1359 parts of Naphthol AS type pigment red, 2000 parts of E-polyester solution of Example 2, 1179 parts of xylol, and 136 parts of wetting agent mixture, consisting of one third alkyl aryl polyether alcohol, one third zinc naphthenate and one third soya lecithin. A color concentrate is prepared by mixing 59 parts of the emulsion of Example 7, 2.9 parts of polychloroprene latex 60% N. V., 12 parts of water, parts of xylol, and adding thereto slowly, under proper agitation a mixture of 30.2 parts of the here described red pigment grind and 0.9 part of a sodium salt of alkylated aryl polyether sulfonate, as emulsifying agent. The pigment grind is thereby emulsified into the binder emulsion. The resulting product is homogenized by passing it through a colloid mill.

Example 10 The product of Example 9 is repeated with the alteration, that the binder emulsion is an emulsion aggregated mixture of 90% E-polyester resin solution of Example 2 and 10% of a butyl modified melamine formaldehyde resin, containing 50% N. V., 30% xylol and butyl alcohol. A suitable product is Melmac 245-8. The presence of the melamine resin increases toughness of the film deposited as a print.

Examples 11 to 14 show the preparation of clear extender print pastes suitable to adjust the color strength of the color concentrates of this invention. The color concentrates and the extender print pastes can be mixed in various proportions to yield cuts of varying color strength. Cuts from 1 to 1 up to 1:200 are normally used.

Example 11 5.90 parts of the emulsion of Example 7, 47.05 parts of a 3% water solution of 4000 cps., methyl cellulose, 47.05 parts of water are mixed and homogenized. Under agitation .with a suitable mixer, like the Eppenbach Homomixer, 100 parts of mineral spirits are stirred into the former emulsion in increments. The mineral spirits used in this example has a bulking value of 0.1515 point of 100 F., a

' This is mixed with a Kauri-Butanol value of 44 to 46, and is marketed under the trade name of Amsco Mineral Spirits #46.

Example 12 To make an extender print paste similar to Example 11, but where the volumetric relation of solvent to water phase is changed to yield a lower solvent percentage: 23.563 parts of a 3% methylcellulose solution in water, using 4000 cps. methylcellulose, 23.563 parts of water and 2.874 parts of concentrated resin emulsion of Example 7, are mixed and 45.710 parts of mineral spirits of Example 11 are incorporated in a manner as described in Example 11. The resulting emulsion has a somewhat lower viscosity than the product of Example 11. This extender emulsion has about 0.739% methylcellulose, 48.499% water, 47.759%- of solvent and 3.003% re-inforcing concentrated resin emulsion.

Example 13.--Reszn-free extender paste 0.750 part of 4000 cps. high Viscosity methylcellulose is dissolved in 49.250 parts of water. 50 parts of mineral spirits of Example 11 is incorporated in increments, under proper agitation. A viscous print paste is obtained.

Example 14.E:rtender print paste of Example 11, where one half of methyl cellulose is replaced by water 0.353 part of 4000 cps. high viscosity methylcellulose is dissolved in 46.773 parts of water, yielding an 0.75% methyl-cellulose solution. concentrated oil-in-water resin emulsion of Example 7, taking 2.874 parts of the latter. The resulting product is agitated and 50 parts of mineral spirits of Example 11 are incorporated in increments under proper agitation. The 50% lower content in high viscosity methylcellulose, its water phase and consequently the emulsion has lower viscosity. The product is a fluid viscous emulsion with good printing qualities.

Other extender print pastes, suitable in this invention are described in my co-pending application Ser. No. 180,700. The concentrated resin emulsions in Examples 11, 12, and 14, and in the examples of my co-pending application Ser. No. 180,700 may be replaced by other concentrated emulsions described elsewhere in this specification.

Example 15.-.S'chematic formula for a concentrateal resin emulsion In this example a schematic formula is given to prepare a concentrated resin emulsion suitable in this invention. Resin examples are also listed, which can be satisfactorily used in this schematic Mixture of 50% water 5.40 Low viscosity methylcellulose solution, as

below 15.44 Hydrogen peroxide 30% 3 54 Total 100.00

Non-volatile content 28-29%.

DRIER MIXTURE FOR SCHEMATIC FORMULA Lead naphthenate, 24%; metal content sol., 200

parts b. w.

Cobalt naphthenate, 6%;

parts b. w.

Zinc naphthenate, 6%;

parts '0. W.

CASEIN SOLUTION FOR SCHEMATIC FORMULA Casein, dry, 7.75 parts b. w. (Protovac 8397) Water, 31 parts b. w.

Dowicide A, 0.0775 parts b. w.(1% on casein) Dowicide G, 0.0775 parts b. w. (1 on casein) Ammonia, conc, 0.1168 parts b. w. (1 on casein) metal content sol., 25

metal content 501., 30

Methylcellulose solution may be present before hydrogen peroxide addition. If e. g. sodium carboxymethylcellulose (CMC) replaces methylcellulose it is preferable to add it after hydrogen peroxide addition.

RESI'NS SUITABLE FgfflSCHElVIATIC FORMULA 1. Epitex 120, bis-phenol epichlorhydrin condensation product esterified with dehydrated castor oil fatty acids. Suitable similar resins can be made by esterifying the condensate (like Epon 1004) with a mixture of 90% soyabean oil fatty acids and oiticica oil fatty acids, or with a mixture of 85% soyabean oil fatty acids and oiticica oil fatty acids.

. Styresol 4250, styrenated fatty acid modified phthalic alkyd.

. BJS 502 Phthalic anhydride-free styrenated alkyds, soya fatty acid esters of 4. RJS 153 carbic anhydride. Polystyrene content to 75%, reduced to 5. RPS 155 N. V.

6. Esskol, Pentaerythritol-glycerin mixed ester of maleic anhydride treated linseed oil fatty acids. Bodied to pass the ammonia test, about 1 hr. between 450-520 F., diluted with solvents to 50% N. V.

7. Keltrol 60, styrenated soyabean oil, diluted to 8. Ail modified phthalic anhydride glycerin alkyd resin with 50-55% oil content, 50% N. V., various suppliers.

Solvents used in above resins are aromatic and/ or aliphatic hydrocarbons.

10 to 20% of resin solution in the schematic example, may be replaced with amine-aldehyde resins, which contain 50% N. V. in solvent mixture of alcohols and hydrocarbons, e. g.:

Melmac 245-8, butyl modified melamine formaldehyde resin Melmac 248-8, butyl modified melamine formaldehyde resin Ufo'rmite MM butyl modified melamine formaldehyde resin Uformite MX61 alkyl modified triazine resin 16 Uformite F240 alkyl modified urea formaldehyde resin Beetle 216-8 alkyl modified urea formaldehyde resin The same emulsions with the resins described above, can be prepared Without emulsion polymerization, using water instead of the hydrogen peroxide in the schematic formula. Such emulsions are similar in nature to the one described in Example 3. The films they form will have a shorter life and the film formation period will be longer, than compared with the emulsion polymerized product.

Example 16.--Schemdtic formulation of pigment color concentrates In the schematic formula for pigment color concentrates I prefer to use 59 parts of concentrated resin emulsion of Example 15, 2.9 parts of polychloroprene latex, 60% nonvolatile, like neoprene 601 latex and pigments in proportions of 7-9% pigment content in the color concentrate The pigments may be incorporated in a manner described in Example 5, using pigment dispersions in water similar to that of Example 4.

The following pigments may be used satisfactorily: Yellow: Benzidine Yellow; Orange: Benzidine Orange; Green: Phthalocyanine Green; Blue: Phthalocyanine Blue; or Indanthrene Blue; Maroon: Thioindigo Maroon; Red: various insoluble azo pigments of the Naphthol AS type couplings; or Thioindigo Reds and Pinks; Brown: various azo browns and vat browns; Greys and Blacks: Carbon Black, such as furnace blacks and channel blacks, gas blacks, bone black, Vegetable black, various vat blacks and greys.

The 59 parts of concentrated emulsion contains about 12.3 parts of resin solids, 2.4 parts of casein, 1.2 parts of low viscosity methylcellulose, 0.7 part of emulsifying agent, and 0.09 part of driers.

In this schematic formula the binder to pigment ratio may be changed in a manner that the binder solids are reduced and the pigment solids increased. Color concentrates with pigment content up to 22% and concentrated resin emulsion content down to 30 to 40% may be suitable for many purposes.

The use of amine-aldehyde resins helps the formation of thermoset resin films and also assists insolubilization of the protective colloids.

Example 17.--Pigment padding Because of the lightfastness of pigments and ease of their application, to obtain solid color effects, pigment padding is becoming more and more popular to replace dyeing. The oil-in-water emulsions of this invention are suitable for pigment padding. The color concentrates of Example 16 may be diluted with Water to the desired color strength. If higher viscosity is required, a mixture of the color concentrate and some extender clear printing paste may be diluted with water. In some cases it is advantageous to add water soluble protective colloids to increase the viscosity of the padding solution. Examples are high viscosity methylcellulose, high viscosity sodium carboxymethylcellulose, sodium or ammonium alginate, amongst others.

In the event.low viscosities can be tolerated, the amount of protective colloid may be reduced in the binder emulsion and color concentrate, whereby laundering resistance increases.

There are two difficulties in the way of popularizing pigment padding. One is crocking. The

binder emulsions, as formulated above, show very low crocking and can be considered as practically non-cracking for many purposes, thereby eliminating this drawback of pigment padding. The second diiiiculty is represented by the phenomenon called pigment migration. During the drying operation the pigments migrate towards the heat and cause streaks and uneven color effects. If the drying tunnels or chambers show the slightest differences in spots with regard to temperature, pigment migration will take place. It is very difficult even with the most modern equipment to have uniform temperatures all over the drying chambers. The emulsion aggregated (emulsion polymerized) binders are solidified in the emulsion and therefore prevent the migration of the pigments. This particular performance of these new emulsions permits their use with great advantage in pigment padding to produce solid color effects by pigments.

Example 18.-Grock reducing agents In the above examples neoprene latex was used as crock reducing agent. I found that satisfactory crock reduction is obtained with the use of neoprene cements (solvent solutions), polystyrene emulsions, Vistanex (linear polymer of isobutylene), vinyl chloride polymers, acrylonitrilecopolymers and mixtures of the last two mentioned polymers. In the use from 0.1% to 2% crock reducing agent solids. In manyinstances increase in the concentrated resin emulsion content may eliminate the necessity of using a special crock reducing agent. The

concentrated resin-binder emulsion may be increased, for example, to about 62% by weight based upon the total composition.

Example 19.-White color concentrate Apigmented white color concentrate is made by preparing a 70% pigment content titanium dioxide water dispersion, by adding 18% Duponol ME and 2% Nekal A (propylated napththalene sulfonate), based on the pigment content. The dispersion contains 70% titanium dioxide, 14% wetting agents and 16% water. The color concentrate is prepared by taking 59 parts of the resin emulsion of Example '7, 2.9 parts of neoprene latex 601, and 38.1 parts of said white pigment slurry (dispersion). This color concentrate may be used to print white on loosely woven fabrics, onlight dyed fabrics, or with a discharge extender cutback emulsion as discharge white on predyed background. A 1:2 cut is a satisfactorydilution. This white pigment concentrate, when added in small proportion; to other colors, will increase their hiding power and enable colored printing eifects on'light or medium light predyed backgrounds, without discharge.

EMULSIONS FOR WOOD FINISHES I have found, that the resin emulsions ofthis invention are particularly suitable as primer undercoats on wood surfaces.

Example 20.Pigmented white undercoat on wood First.-A base varnish is prepared as follows: In 100 parts of Keltrol 60 (Styrenated soyabean oil, 70% N. V. dissolved in hydrocarbon solvent). we dissolve 30 parts of Pentalyn G, which is a pentaerythritol' ester of the maleic adduct of rosin. The maleic resin is dissolved in the Keltrol by the aid of heat.

Second.-An emulsion polymerized varnish emulsion is made} using --the-- following' proporcolor concentrates I may tions: 300 parts base varnish, 4.5 parts drier mixture, 8'7 parts of a 10% Duponol ME solution, 147 parts of a 20% casein solution, 39 parts of a 1:1 mixture of cone. ammonia and water, 51 parts of hydrogen peroxide conc., parts of low viscosity sodium carboxymethylcellulose in water, 20% strong and 36 parts of water, totaling 739.5 parts. Procedure and solutions like in schematic formula of Example 15, except where specified here dilferently.

Third.White pigmented undercoat is prepared by mixing and milling the following composition: 4422 parts of above emulsion polymerized varnish emulsion, 16 parts of RV-62, a coated resin soap flatting agent. 56.8 parts of Geon 11X latex, a 56.3% emulsion of polyvinyl chloride, 45.6 parts of a 70% zinc oxide paste in water, 414 parts of water, 43.6 parts of kaolin clay, 33 parts of mica, 718.4 parts of lithopone (Albalith 362), water dispersible type, parts of diatomaoeous earth, 10 parts of Triton A-20 (nonionic emulsifying and wetting agent) and 10 parts of zinc naphthenate (Nuomix); totaling 1951.8 parts. The 70% zinc oxide paste is made from 70 parts of Kadox zinc oxide, 0.7 part of Darvan and 30 parts of water. Darvan is a pigment dispersing agent and is described as polymerized sodium salts of short chain alkyl naphthalene sulfonic acids.

The resulting product may be applied by brush or spray application, after diluting it to proper viscosity for the particular application with water. The coating dries within 30 minutes and can be recoated within 2 hours with solvent type paints, or water paints. After 30 minutes it can be dry sanded and surface properly smoothened.

The pigment volume in this coating is high and can be reduced, to getv increased toughness. Lower pigment volume coatings sand less satisfactorily.

The varnish emulsion can be prepared from other resins of Example 15 and very satisfactory products can be prepared from the emulsion of Example 7.

. Example 21.-Clear undercoat for wood.

442.2 parts of the emulsion polymerized varnish emulsion of Example 20, 56.8 parts of Geon Latex 11X, as used in Example 20, and 9.2 parts of the 70% zinc oxide paste used in Example 20, are mixed, totaling 508.2 parts. The Geon latex helps to cure after-tack of the film and the zinc oxide stabilizes the polyvinyl chloride. The quantity of zinc oxide is so small, that the coating is transparent and does not cloud the grain design of the wood. This undercoat also may be applied by brush application or by spraying, after it is diluted to proper viscosity by water. It forms a non-penc trating and filling undercoat and seals the pores of the wood from the topcoat. Using this undercoat on Douglas fir plywood or California redwoodplywood and a good quality solvent type varnish as topcoat, a 2-coat smooth finish is ob-' tainable with uniform gloss distribution, whereas by conventional methods a large number of coats are required and still the grain and non-grain portionof the wood will show difference in gloss and light reflectance. Particularly the Cali-.- fornia redwood is very beautiful, on account of its nice grain design, but heretofore no satisfac tory finishing system existed for this surface.

This clear undercoat may be applied under the white undercoat of Example 20 with advantage and prevents-later dvelopedcracks in"'plywood 19 to show through the top finish. Under later developed cracks I :mean cracks formed after .finishing.

Iclaim:

.1. An oi'l-in-Water resin emulsion textile decorating pigment color composition comprising water, between about 4.5% and about 31% of an emulsified resin-binder, between about 0.18% and 2.16% of an emulsifying agent selected from the class consisting of soaps of fatty acids, fatty acid esters of polyethylene glycols, quaternary ammonium salts, fatty aclohol sulfates, polyethyleneoxide' condensation products, polymerized glycol esters and sodium salts of organic sulfonates, between about 0.075% and 4.34% of a protective colloid selected from the class consistingof casein, ammonium caseinate, methylcellulose, sodium carboxymethylcellulose, gum tragacanth, dextrine, starch, sodium acrylate,

sodium methacrylate, water-soluble and alkalisoluble hydroxyethylcellulose, locust beangum, water-soluble salts of the maleic adduct of styrene and alginates, between about 7% and 22% of a dispersed pigment which is a member of the class consisting of phthalocyanine pigments, insoluble azo pigments, vat pigments and carbon blacks,:said emulsified resin-binder comprising a polyunsaturated fatty acid ester of a polyhydrio alcohol in an emulsion polymerized state, the vehicle solids of the emulsion being sensitive to the action of the air, when exposed to it in a thin layer of a wet film thickness of 0.0015 to 0.003, forming a coherent solid film immediately upon demulsification of the emulsion, said solid film formation being reached within a period-ranging from a couple of seconds to one hour, the solid polyhydric alcohol esters forming the dispersed phase of the emulsion having an oxygen content which does not exceed the oxygen content of the unemulsified polyhydric alcohol esters by more than 2.8%, said percents being by weight and being based on the'total composition, said pigment color composition being viscous and being suitable as a color concentrate which is dilutable with clear extender print paste emulsions to form the desired strength of shade when used for textile printing, said fatty acid ester being a member of the class consisting of (i) styrenated alkyd resins comprising fatty acids in the acid component, (ii) styrenated fatty oils and (iii) pentaerythritol-glycerine mixed esters of maleic anhydride treated fatty acids, all of said fatty acids containing polyunsaturated fatty acids.

2. ,A pigment-free oil-inwaer emulsion coating material in which the dispersed phase incorporates a member of the class consisting of (i) styrenated alkyd resins comprising fatty acids in the acid component, (ii) styrenated fatty oils,

(ii-i) pentaerythritol-glycerin mixed esters of maleic anhydride treated fatty acids, all of said fatty acids containing polyunsaturated fatty acids, said member being in a solid state in the water emulsion, the vehicle solids of the emulsion beingsensitive to the action of the air, when exposed to it in a thin layer of a wet film thickness f'0.00l5 to 0.003", forming a coherent solid film immediately upon demulsification of the emulsion, said solid film formation being reached within a period ranging from a couple of seconds to one hour, the solid polyhydric alcohol esters forming the dispersed phase of the emulsion having an oxygen content which does not exceed the oxygen'content of the unemulsified polyhydrjic alcohol esters by more than 2.8%, the

vehicle solids dispersed phase content ranging from 10% to %.,based on the total weight of Water and vehicle solids constituents of the emulsion surface coating material, said emulsion surface coating material comprising further an emulsifying agent selected from the class consisting of soaps of fatty acids, fatty acid esters of polyethylene glycols, quaternary ammonium salts, fatty alcohol sulfates, polyethyleneoxide condensation products, polymerizedglycol esters and sodium salts of organic sulfonates in a proportion between about 0.2% and about 4.2% based on said oil-in-water emulsion, and a protective colloid selected from the class consistin of casein, ammonium caseinate, methylcellulose, sodium carboxymethylcellulose, gum tragacanth, dextrine, starch, sodium acrylate, sodium methacrylate, water-soluble and alkali-soluble hydroxyethylcellulose, locust 'bean gum, water-soluble salts of the maleic adduct of styrene and alginates in a proportion between about 0.25% and about 7% based on said oil-in-water emulsion.

3. An oil-in-water resin emulsion textile deccrating pigment color composition comprising water, between about 4.5% and about 31% of an emulsified resin-binder, between about 0.18% and 2.16% of an emulsifying agent selected from the class consisting of soaps of fatty acids, fatty acid esters of polyethylene glycols, quaternary ammonium salts, fatty alcohol sulfates, polyethyleneoxide condensation products, polymerized glycol esters and sodium salts of organic sulfcnates, between about 0;075% and 4.34% of a protective colloid selected from the class consis'tihg of casein, ammonium caseinate, methylcellulose, sodium carboxymethylcellulose, gum tragacanth, dextrine, starch, sodium acrylate, sodium methacrylate, water-soluble and alkalisoluble hydroxyethylcellulose, locust bean gum, water-soluble salts of the maleic adduct of styren-e and alginates, between about 7% and 22% of a dispersed pigment which is a member of the class consisting of phthalocyanine pigments, insoluble azo pigments, vat pigments and carbon blacks, said emulsified resin-binder comprising a polyunsaturated fatty acidester of a polyhydric alcohol, said ester being a member of the class consisting of (i) styrenated alkyd resins comprising fatty acids in the acid component, (ii) styrenated fatty oils and (iii) pentaerythritolglycerin mixed esters of maleic anhydride treated fatty acids, the polystyrene content of (i) ranging from 25% to of resin solids, said percents being by weight and being based on the total composition except where otherwise stated in this claim, said pigment color composition being viscous and being suitable as a color concentrate which is dilutable with clear extender printpaste emulsions to form the desired strength of shade when used for textile printing.

4. The composition of claim 3, in which the resinous binder is a styrenated fatty acid modified alkyd resin.

5. The composition .of claim 3, in which the resinous binder is a styrenated fatty acid modified alkyd resin comprising phthalic anhydride in the polycarboxylic acid component of the resin.

6. The composition of claim 3, in which the resinous binder is a styrenated fatty acid modified alkyd resin comprising bi-cyclo'2-21 cycloheptane delta .5 .dicarboxylic anhydride 2,3 in the polycarboxylic acid constituent and having a 21 polystyrene content of from 25% to 75% of the resin solids.

7. The composition of claim 3, in which the resinous binder comprises pentaerythritol in the ester forming polyhydric alcohol component and the condensation product of maleic anhydride and polyunsaturated fatty acids in the fatty acid component.

8. The composition of claim 3, in which the resinous binder comprises a styrenated fatty acid ester.

9. The composition of claim 3, in which the resinous binder non-volatile content comprises from about 10% to about 20% of an organic solvent amine-formaldehyde resin.

10. The composition of claim 3, in which the resinous binder non-volatile content comprises from about 10% to about 20% of an organic solvent soluble melamine-formaldehyde resin.

11. The composition of claim 3, in which the resinous binder non-volatile content comprises from about 10% to about 20% of an organic solvent soluble urea-formaldehyde resin.

12. The composition of claim 3, containing in addition organic volatile hydrocarbon solvents in the dispersed phase of the emulsion.

13. An oil-in-water resin emulsion textile printing color composition consisting of 1 part by volume of the color concentrate of claim 3 and from about 1 part to about 200 parts by volume of a clear extender print paste emulsion, said extender print paste emulsion comprising N to 56% water, 0.3% to 0.8% of high viscosity water soluble cellulose ether and 43% to fal of a Water immiscible hydrocarbon solvent, all percents being by weight.

14. The textile decorating pigment color composition of claim 3, in which the pigment is an inwater deflocculated dispersed pigment, and its particles are surrounded by water.

15. The textile decorating pigment color composition of claim 3, in which the pigment is an in-resin defiocculated dispersed pigment, and its particles are surrounded by the resin-binder.

16. The composition of claim 3, in which the emulsifying agent is a lauryl alcohol sulfate.

17. A discontinuously decorated printed textile fabric on which the color is a deposit comprising a colored pigment and an emulsion polymerized resinous binder which is a polyunsaturated fatty acid ester of a, polyhydric alcohol, said deposit comprising the non-volatile content of the composition of claim 1.

13. A continuously decorated pad-dyed textile fabric in which the color is a deposit comprising a colored pigment and an emulsion polymerized resinous binder which is a polyunsaturated fatty acid ester of a polyhydric alcohol, said deposit comprising the non volatile content of the composition of claim 1.

19. The textile decorating pigment color composition of claim 3, in which the pigment is an inwater deflocculated dispersed pigment, and its particles are surrounded by water, in which composition there is contained about 20% pigment dispersing agent based on the dry pigment content.

20. The textile decorating pigment color composition of claim 3, in which the pigment is an in-water defiocculated dispersed pigment, and its particles are surrounded by Water, in which composition there is contained about 20% pigment dispersing agent based on the dry pigment content, and said pigment dispersing agent comprising 9, lauryl alcohol sulfate.

References Cited in the file of this patent UNITED STATES PATENTS 

1. AN OIL-IN-WATER RESIN EMULSION TEXTILE DECORATING PIGMENT COLOR COMPOSITION COMPRISING WATER, BETWEEN ABOUT 4.5% AND ABOUT 31% OF AN EMULSIFIED RESIN-BINDER, BETWEEN ABOUT 0.18% AND 2.16% OF AN EMULSIFYING AGENT SELECTED FROM THE CLASS CONSISTING OF SOAPS OF FATTY ACIDS, FATTY ACID ESTERS OF POLYETHYLENE GLYCOLS, QUATERNARY AMMONIUM SALTS, FATTY ALCOHOL SULFATES, POLYETHYLENEOXIDE CONDENSATION PRODUCTS, POLYMERIZED GLYCOL ESTERS AND SODIUM SALTS OF ORGANIC SULFONATES, BETWEEN ABOUT 0.075% AND 4.34% OF A PROTECTIVE COLLOID SELECTED FROM THE CLASS CONSISTING TO CASEIN, AMMONIUM CASEINATE, METHYLCELLULOSE, SODIUM CARBOXYMETHYLCELLULOSE, GUM TRAGACANTH, DEXTRINE, STARCH, SODIUM ACRYLATE, SODIUM METHACRYLATE, WATER-SOLUBLE AND ALKALISOLUBLE HYDROXYETHYLCELLULOSE, LOCUST BEAN GUM, WATER-SOLUBLE SALTS OF THE MALEIC ADDUCT OF STYRENE AND ALIGINATES, BETWEEN ABOUT 7% AND 22% OF A DISPERSED PIGMENT WHICH IS A MEMBER OF THE CLASS CONSISTING OF PHTHALOCYANINE PIGMENTS, INSOLUBLE AZO PIGMENTS, VAT PIGMENTS AND CARBON BLACKS, SAID EMULSIFIED RESIN-BINDER COMPRISING A POLYUNSATURATED FATTY ACID ESTER OF A POLYHYDRIC ALCOHOL IN AN EMULSION POLYMERIZED STATE, THE VEHICLE SOLIDS OF THE EMULSION BEING SENSITIVE TO THE ACTION OF THE AIR, WHEN EXPOSED TO IT IN A THIN LAYER OF A WET FILM THICKNESS OF 0.0015" TO 0.003", FORMING A COHERENT SOLID FILM IMMEDIATELY UPON DEMULSIFICATION OF THE EMULSION, SAID SOLID FILM FORMATION BEING REACHED WITHIN A PERIOD RANGING FROM A COUPLE OF SECONDS TO ONE HOUR, THE SOLID POLYHYDRIC ALCOHOL ESTERS FORMING THE DISPERSED PHASE OF THE EMULSION HAVING AN OXYGEN CONTENT WHICH DOES NOT EXCEED THE OXYGEN CONTENT OF THE UNEMULSIFIED POLYHYDRIC ALCOHOL ESTERS BY MORE THAN 2.8%, SAID PERCENTS BEING BY WEIGHT AND BEING BASED ON THE TOTAL COMPOSITION, SAID PIGMENT COLOR COMPOSITION BEING VISCOUS AND BEING SUITABLE AS A COLOR CONCENTRATE WHICH IS DILUTABLE WITH CLEAR EXTENDER PRINT PASTE EMULSIONS TO FORM THE DESIRED STRENGTH OF SHADE WHEN USED FOR TEXTILE PRINTING, SAID FATTY ACID ESTER BEING A MEMBER OF THE CLASS CONSISTING OF (I) STYRENATED ALKYD RESINS COMPRISING FATTY ACIDS IN THE ACID COMPONENT, (II) STYRENATED FATTY OILS AND (III) PENTAERYTHRITOL-GLYCERINE MIXED ESTERS OF MALEIC ANHYDRIDE TREATED FATTY ACIDS, ALL OF SAID FATTY ACIDS CONTAINING POLYUNSATURATED FATTY ACIDS. 